Sulfoderivatives of 1-aminonaphthalene-8-carboxylic acid and process of making the same



Patented Oct. 28, 1930.

UNITED STATES PATENT OFFICE mam RICHARD HERZ AND FRITZ SCHUL'IE, OF FneNKroRnoN-rHn AIn, GERMANY, AS-

sIGNoRs T0 GENERAL .ANILINE wonns, Inc... NEW YORK; N. Y., A con-rone'rron OF DELAWARE SULFODERIVATIVES or 1-AMinonnrrizrrmrinnnacnnsoxymcnew AND PROCESS or p MAKING THE srnvrn 1 No Drawing. Original application filed November 23, 1926, Serial No. 151,596, and in Germany December 4, 1925. Divided and this application filed November 1'7, 1927. Serial No. 234,035.

This application is a divisionof our applicationSerial Number 151,596, filed November 29, 1926, which has matured into .Patent No. 1,728,995,'dated Sept. 24;, 1929. p 5 In application Serial No. 122,030, dated July 12, 1926, a new and original process for manufacturing the 1-aminonaphthalene-8- carboxylicacid is described, .which consists in allowingto react at elevated temperatures an alkaline acting agent.v on the S-cyannaphthalene-l-sulfonic acid.

"This process is not limited tothe S -cyannaphthalene-l-sulfonic acid, but also applicable to its nuclear substitution products, particularly to halogenated derivatives and those containing further sulfonic groups in the nucleus. These nuclearderivatives of the 8-cyannaphthalene-l-sulfonic acid 1 are readily obtainable by diazotizing the :8-amino-naphthalenel-sulfonic acids corre- L spondingly substituted in the nucleons and treating the diazobodies', thus produced, with cuprous "cyanide, according to the Sandmeyer reactionf v T Incarryingout our process practically all 'methods may be applied, which are described in the above mentioned application, particularly caustic alkalies in aqueous or alcoholic.

solution or alkaline. earths, preferably milk sure or ina closed vessel at elevatedpressure are obtainable eitherderivatives of l-aminonaphthalene8 carboxysulfonic 'acid havingthe probable formula: I

i nooc Nun eersor sulfonic acids of naphthostyril having the probable formula: v a 7 i vco--Nn of lime may .bepused, either at ordinary presr In order to They 1 9 resented by the following general formula:

wherein Y represents an amino group and Z a carboxylic acid group, or Y and Z jointly represent the group The sulfonic acid group may be bound many tionadvantageously in the presence of an alcohol-at temperatures not substantially 6X Under mild conditions,

ceeding' 135 (1., or when treating with milk o'f-limein a closed vessel, generally the sulfonic acid derivatives of naphthos'tyril respectively of the l-aminonaphthalene-8-car boxylic acid result, whereas at more elevated temperatures the s'ulfonic acid derivatives of the first phase ofthe reaction are converted into the corresponding hydroXy compounds. These latter can be alkylated by means of alkylating agents and the formed alkoxyn'aphthostyrils can be saponified to the cor- 1 responding alkoxyderivatives of the l-aminonaphthalene-S-carbQXylic acid.

" All these sulfonic acid, hydroXy-i and. alkoxy derivatives of the l-aminonaphtha- Iene-S carboXyIic acid are new compounds, not described hitherto in literature. They are of particular valueas intermediates for the.

production of dyesturfs andjpharmaceutic'al compounds.

further illustrate our inven: tion the followingexamples are given,the parts being by weight and all temperatures centigrade degrees, but. it is understood that our invention is not limited to the particular products or reaction conditions mentioned therein:

E wample 1 4 partstof caustic potash and 5 parts of methylic alcohol are heated for some time at 80-100 while stirring; at this temperature 1 part of the sodium salt of the S-cyannaph thalene-LG-disulfonic acid, derived from S-aminonaphthalene-l-.6'disulfonic acid by Sandmcycrs reaction, is added. Then methylic alcohol is slowly distilled off, until the ten'ipcrature of the mass rises to about 135. At this temperature heating is continued for some hours under reflux. Then the mass is cooled down, diluted with water and gently acidified while cooling. With a strong evolution of sulfurous acid a new compound separates, which has probably the chemical constitution of the l-aminonaphthalene-8- carboxylic-G-sulfonic acid of the formula:

HOOC

CO-NH E mample 93 1 part of the sodium or any suitable salt 01 the S-cyannaphthalene-Ltlrdisultonic acid is heated with parts of milk of lime of 136. for some hours at 200--250 in an autoclave while stirring. After cooling down the mass is acidified and the separated l-aminonaphthaIene-S-carbOXylic 6 suli'onic acid is filtered and purified by dissolving it in a solution of sodium carbonate, filtering this solution and working in the autoclave, the pressure corresponds functionally to the tension of the reacting agent and the temperature applied.

We claim: 1. The process which comprises reacting under mild conditions with an alkaline agent upon a nuclear substitution product of S-cyannaphthalene-l-sulfonic acid containing a further sulfonic acid group in the nucleus in B-position.

2. The process which comprises reacting with milk of lime at a temperature higher c the S0111 grou standing H018 in B-positlon,

wherein Y represents an amino group and Z a carboxylic acid group, or Y and Z jointly represent the group co-NH,

being in the open form, when dry, colorless powders soluble in dilute soda solution, diazotizable and capable of combining with diam-compounds, and in the form of their anhydrides being yellowish powders neither diazot-izable nor capable of combining with diazo-compounds. a i

4. As a new product the compound of the general formula wherein Y represents an amino group and Z a carboxylic acid group, or Y and Z jointly represent the group CON H,

being in the open form, when dry, a colorless powder soluble in dilute soda solution, diazotizable and capable of combining with diazocompounds, and in the form of its anhydride being a yellowish powder neither diazotizable nor capable of combining with diazo-compounds.

In testimony whereof, we aifix our signatures. I

RICHARD HER-Z. FRITZ SGHULTE. 

